JPH07286514A - Gripping material for exhaust emission control device - Google Patents
Gripping material for exhaust emission control deviceInfo
- Publication number
- JPH07286514A JPH07286514A JP7763994A JP7763994A JPH07286514A JP H07286514 A JPH07286514 A JP H07286514A JP 7763994 A JP7763994 A JP 7763994A JP 7763994 A JP7763994 A JP 7763994A JP H07286514 A JPH07286514 A JP H07286514A
- Authority
- JP
- Japan
- Prior art keywords
- gripping material
- fiber
- catalyst
- fibers
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Exhaust Gas After Treatment (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は内燃機関の排ガス浄化装
置に用いる触媒把持材に関するものであり、特にハニカ
ム型触媒を触媒ケーシング内に保持するための把持材に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst gripping material used in an exhaust gas purifying apparatus for an internal combustion engine, and more particularly to a gripping material for holding a honeycomb type catalyst in a catalyst casing.
【0002】[0002]
【従来の技術】内燃機関の排ガス中に含まれる窒素酸化
物を除去するために、排ガスの流路に触媒ケーシング内
にハニカム型触媒を収容した浄化装置を設置することが
行われている。自動車ではマフラーを触媒ケーシングと
し、マフラー内部にセラミック製触媒を収容して浄化装
置としている。このハニカム型触媒をマフラー内に安定
に保持させるために、セラミック繊維又はセラミック繊
維中に熱膨張性鉱物片を分散させ、有機バインダー等で
固めた成形体(以下、鉱物含有成形体)を把持材として
用いることが提案されている(特開平1−240715
号公報参照)。2. Description of the Related Art In order to remove nitrogen oxides contained in the exhaust gas of an internal combustion engine, a purifying device in which a honeycomb type catalyst is housed in a catalyst casing is installed in the exhaust gas passage. In automobiles, a muffler is used as a catalyst casing, and a ceramic catalyst is housed inside the muffler to form a purification device. In order to stably hold this honeycomb-type catalyst in the muffler, a ceramic fiber or a thermally expandable mineral piece dispersed in the ceramic fiber, and a molded body (hereinafter, mineral-containing molded body) solidified with an organic binder or the like is used as a gripping material. Has been proposed (JP-A-1-240715).
(See the official gazette).
【0003】これらの把持材に使用されるセラミック繊
維としてはシリカ繊維、アルミナ−シリカ繊維、石綿繊
維、ガラス繊維、ジルコニア−シリカ繊維等が知れてい
る。ディーゼルエンジンでは排ガス中に多量のすすを含
んでいるため、マフラー部で一旦このすすを集塵した
後、マフラー内で高温加熱処理することですすの燃焼お
よび除去をおこなっている。そのためハニカム型触媒や
把持材は800〜1000℃の高温にさらされることに
なる。このような高温下では、従来の把持材に使用され
ているセラミック繊維では、結晶粒の発生、結晶成長に
よる繊維の脆化が起こり、把持能力の低下する恐れがあ
った。Silica fibers, alumina-silica fibers, asbestos fibers, glass fibers, zirconia-silica fibers and the like are known as ceramic fibers used for these holding materials. Since a diesel engine contains a large amount of soot in the exhaust gas, the soot is once collected in the muffler and then heated and heated in the muffler to burn and remove it. Therefore, the honeycomb type catalyst and the holding material are exposed to a high temperature of 800 to 1000 ° C. Under such a high temperature, in the ceramic fiber used in the conventional gripping material, generation of crystal grains and brittleness of the fiber due to crystal growth may occur, and the gripping ability may be deteriorated.
【0004】[0004]
【発明が解決しようとする課題】本発明は高温下におい
ても繊維の脆化が起きず、有機バインダー等を燃焼除去
する手間のかからないハニカム型触媒の把持材を提供す
ることを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a honeycomb catalyst gripping material which does not cause embrittlement of fibers even at high temperatures and which does not require combustion and removal of organic binders.
【0005】[0005]
【課題を解決するための手段】本発明は、強度が大きく
かつショット含有率の少ないムライト組成のアルミナ繊
維からなるニードルパンチングを施したブランケットを
把持材として用いると、復元力に優れかつ劣化が起こり
にくいとの知見に基づいて達成されたものである。本発
明について詳細に説明すると、本発明の把持材はアルミ
ナ繊維の積層体からなる。積層体を構成するアルミナ繊
維は、その繊維長、繊維径は特に限定されないが、通
常、繊維長は20〜200mm、繊維径は1〜40μ
m、好ましくは2〜20μmである。この繊維は、Al
2 O3 /SiO2 重量比(以下、Al2O3 /SiO2
という)=70/30〜74/26のムライト組成であ
ることが必要である。Al2 O3 /SiO2 が上記範囲
外のアルミナ繊維では、高温時の結晶化および結晶成長
による繊維の劣化が早く、長期の使用に耐えられない。According to the present invention, when a needle punched blanket made of alumina fiber having a mullite composition having a high strength and a low shot content is used as a gripping material, excellent resilience and deterioration occur. This was achieved based on the finding that it is difficult. Explaining the present invention in detail, the holding material of the present invention comprises a laminated body of alumina fibers. The fiber length and the fiber diameter of the alumina fiber constituting the laminate are not particularly limited, but usually the fiber length is 20 to 200 mm and the fiber diameter is 1 to 40 μm.
m, preferably 2 to 20 μm. This fiber is Al
2 O 3 / SiO 2 weight ratio (hereinafter referred to as Al 2 O 3 / SiO 2
) = 70/30 to 74/26. Alumina fibers whose Al 2 O 3 / SiO 2 is out of the above range are not able to withstand long-term use due to rapid deterioration of the fibers due to crystallization and crystal growth at high temperatures.
【0006】本発明で用いるムライト組成のアルミナ繊
維は、結晶化度が0〜10%であるのが好ましい。ここ
で、結晶化度とは1300℃で4時間焼成して完全に結
晶化したムライトのCuKα線によるX線回折における
2θ=26.3°に発現するピークの強度に対する、ム
ライト組成アルミナ繊維の2θ=26.3°のピーク強
度を百分率(%)で表したものである。ムライト組成の
アルミナ繊維は他の組成のアルミナ繊維に比べ、高温に
加熱した時、結晶粒が発生しにくいが、特に結晶化度が
0〜10%と低結晶性のムライト組成アルミナ繊維は、
結晶成長の核となる結晶が少ないため、800〜100
0℃の加熱によっても繊維の劣化が生じにくい。The alumina fiber having a mullite composition used in the present invention preferably has a crystallinity of 0 to 10%. Here, the crystallinity means 2θ of the mullite composition alumina fiber with respect to the intensity of the peak appearing at 2θ = 26.3 ° in X-ray diffraction by CuKα ray of mullite completely crystallized by firing at 1300 ° C. for 4 hours. The peak intensity at 26.3 ° is expressed as a percentage (%). Alumina fibers having a mullite composition are less likely to generate crystal grains when heated to a higher temperature than alumina fibers having other compositions, but in particular, a mullite composition alumina fiber having a low crystallinity of 0 to 10% is
Since there are few crystals that are the nucleus of crystal growth, 800 to 100
Deterioration of the fiber hardly occurs even by heating at 0 ° C.
【0007】本発明に用いるアルミナ繊維の単繊維引張
強度は、150〜400kg/mm 2 である。150k
g/mm2 に満たないと把持具としての十分な面圧が得
られない。単繊維引張強度は大きいほど把持材の強度が
大きくなるので好ましいが、400kg/mm2 を超え
ると繊維がしなやかさを欠き、把持材はもろくなる。ま
た、本発明で使用するアルミナ繊維は、粒径45μm以
上のショットの含有率が5重量%以下である。粒径45
μmに満たないショットは、把持材内に存在しても復元
力等に影響は与えないが、粒径45μm以上のショット
は、それをてこの支点とする繊維の切断を起こし、把持
材の復元力を損う。また、粒径45μm以上のショット
の含有率が5重量%をこえると、把持材の比重を部分的
に増大させ、熱伝導率等が不均一となり、ハニカム型触
媒を均一に把持できなくなる。Single Fiber Tensile of Alumina Fiber Used in the Present Invention
Strength is 150-400 kg / mm 2Is. 150k
g / mm2If it is less than the specified value, sufficient surface pressure as a gripping tool can be obtained.
I can't. The higher the single fiber tensile strength, the stronger the gripping material.
400kg / mm although it is preferable because it becomes large2Beyond
Then, the fiber lacks flexibility and the gripping material becomes brittle. Well
The alumina fiber used in the present invention has a particle size of 45 μm or less.
The content of the upper shot is 5% by weight or less. Particle size 45
Shots less than μm are restored even if they exist in the gripping material
Shots with a particle size of 45 μm or more, although they do not affect the force, etc.
Causes the fiber to be cut by using it as a fulcrum and grips it.
Impairs the resilience of the material. Also, shots with a particle size of 45 μm or more
If the content of slag exceeds 5% by weight, the specific gravity of the gripping material will be partially
To a non-uniform thermal conductivity, the honeycomb type
The medium cannot be held uniformly.
【0008】アルミナ繊維を積層したブランケットは、
一般に知られているブランケットの製造法により製造す
ることができ、例えば、オキシ塩化アルミ等のアルミナ
源、シリカゾル等のシリカ源、ポリビニルアルコール等
の有機バインダー及び水を混合後、紡糸して得られたア
ルミナ繊維前駆体を積層したシートにニードルパンチン
グを施した後、1000〜1300℃で焼成することに
より得られる。A blanket laminated with alumina fibers is
It can be produced by a generally known blanket production method. For example, it is obtained by mixing an alumina source such as aluminum oxychloride, a silica source such as silica sol, an organic binder such as polyvinyl alcohol and water and spinning the mixture. It is obtained by needle-punching a sheet in which alumina fiber precursors are laminated and then firing at 1000 to 1300 ° C.
【0009】ニードルパンチングを施すことにより、シ
ート内のアルミナ繊維前駆体の一部がシートを貫通して
縦方向に配向してシートを緊縛するため、シートの嵩比
重を高めることができ、また、層間の剥離、層間のずれ
を防止することができる。ニードルパンチングの密度は
通常1〜50打/cm2 であり、ニードルパンチングの
密度を変化させることにより、ブランケットの嵩比重や
強度を調節することができる。(特開昭62−1706
0号公報参照) 本発明の把持材を用いてハニカム型触媒を触媒ケーシン
グ内に把持するには、例えば、ハニカム型触媒の全周
に、把持材を均一な厚さとなるようにきつく巻きつけ、
触媒ケーシング内に収容して、把持材の復原力によりケ
ーシング内壁に密着して固定されるようにすればよい。By performing needle punching, a part of the alumina fiber precursor in the sheet penetrates the sheet and is oriented in the longitudinal direction to bind the sheet, so that the bulk specific gravity of the sheet can be increased. It is possible to prevent peeling between layers and displacement between layers. The density of needle punching is usually 1 to 50 strokes / cm 2 , and the bulk specific gravity and strength of the blanket can be adjusted by changing the density of needle punching. (JP-A-62-1706
In order to hold the honeycomb type catalyst in the catalyst casing using the holding material of the present invention, for example, the holding material is tightly wound around the entire circumference of the honeycomb type catalyst so as to have a uniform thickness,
It may be housed in the catalyst casing so that it is fixed in close contact with the inner wall of the casing by the restoring force of the gripping material.
【0010】[0010]
【実施例】次に、実施例により本発明を具体的に説明す
るが、本発明はその要旨を超えない限り、以下の実施例
によって限定されるものではない。 実施例1 800℃、24時間の加熱による繊維の劣化をみるた
め、表−1に示す性質を有し、繊維径約4μm、45μ
m以上のショットを4%含有する繊維からなり、ニード
ルパンチングを施したブランケット25gを水1.5l
に分散させ、家庭用ミキサーで所定時間解繊し、30分
放置後、沈降体積を測定した。繊維が劣化すると、解繊
により繊維は折れて短くなり、沈降体積は小さくなるの
で、熱処理前後の沈降体積を比較すると、熱処理による
劣化の程度が分る。結果を表−1に示す。EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. Example 1 In order to observe the deterioration of the fiber due to heating at 800 ° C. for 24 hours, the fiber has the properties shown in Table-1, and the fiber diameter is about 4 μm and 45 μm.
25 g of needle-punched blanket made of fiber containing 4% of shots of m or more, and 1.5 l of water.
And disintegrated with a household mixer, defibrated for a predetermined time, allowed to stand for 30 minutes, and then measured sedimentation volume. When the fiber is deteriorated, the fiber is broken and shortened due to the defibration, and the sedimentation volume becomes small. Therefore, when the sedimentation volume before and after the heat treatment is compared, the degree of deterioration due to the heat treatment can be known. The results are shown in Table-1.
【0011】比較例1 表−1に示す性質を有し、繊維径約4μmの繊維からな
り、ニードルパンチングを施したブランケットを用いた
他は実施例1と同様に行った。結果を表−1に示す。Comparative Example 1 The procedure of Example 1 was repeated except that a blanket having the properties shown in Table 1 and having a fiber diameter of about 4 μm and having needle punching was used. The results are shown in Table-1.
【0012】比較例2 表−1に示す性質を有し、繊維径約3μmのセラミック
繊維からなり、ニードルパンチングを施したブランケッ
トを用いた他は実施例1と同様に行った。結果を表−1
に示す。Comparative Example 2 The same procedure as in Example 1 was carried out except that a blanket having a property shown in Table 1 and made of ceramic fiber having a fiber diameter of about 3 μm and having needle punching was used. The results are shown in Table-1
Shown in.
【0013】[0013]
【表1】 [Table 1]
【0014】表−1より、単繊維引張強度が150kg
/mm2 に満たない繊維では、熱処理を施す前において
も沈降体積が小さく、繊維が折れ易いことが分かる。ま
た、単繊維引張強度が150kg/mm2 以上であって
も、45μm以上のショットの含有率が5重量%を超え
ると、熱処理を施すと折れの発生が顕著であることが分
かる。From Table 1, the single fiber tensile strength is 150 kg.
It can be seen that the fibers having a ratio of less than / mm 2 have a small sedimentation volume even before the heat treatment, and the fibers are easily broken. Further, even if the single fiber tensile strength is 150 kg / mm 2 or more, if the content of shots of 45 μm or more exceeds 5% by weight, it is found that the occurrence of breakage is remarkable when heat treatment is performed.
【0015】実施例2 実施例1と同じ繊維からなり、面密度0.160g/c
m2 であるニードルパンチングが施されているブランケ
ットから、縦50×横50(mm)の直方体の試料片を
切り出して、高温と低温のくりかえしによる面圧の変
化、即ち、把持力の変化を調べるためのサイクル試験を
行った。面密度は密度×厚さで算出される値である。結
果を表−2に示す。Example 2 Made of the same fiber as in Example 1 and having an areal density of 0.160 g / c.
A rectangular parallelepiped sample piece of 50 mm x 50 mm is cut out from a blanket on which needle punching of m 2 is applied, and changes in surface pressure due to repeated high and low temperatures, that is, changes in gripping force are investigated. A cycle test was performed. The areal density is a value calculated by density × thickness. The results are shown in Table-2.
【0016】サイクル試験 1.室温において、試料片を厚み方向に4.6mmまで
圧縮し、面圧を測定する。 2.次いで、該試料片の厚みを4.9mmまで拡張しな
がら、試料片の中央部が800℃になるよう加熱する。
試料片の中央部が800℃になった時点で面圧を測定す
る。 3.面圧を測定しながら、800℃で1時間保持する。 4.該試料片の厚みを4.6mmまで圧縮しながら、放
冷する。 5.1〜4を1サイクルとし、3回くりかえす。Cycle test 1. At room temperature, the sample piece is compressed to 4.6 mm in the thickness direction, and the surface pressure is measured. 2. Next, the thickness of the sample piece is increased to 4.9 mm, and the center portion of the sample piece is heated to 800 ° C.
The surface pressure is measured when the central portion of the sample piece reaches 800 ° C. 3. Hold the surface pressure at 800 ° C. for 1 hour while measuring the surface pressure. 4. The sample piece is allowed to cool while being compressed to a thickness of 4.6 mm. Repeat 1 to 4 as one cycle and repeat 3 times.
【0017】比較例3 ハニカム型触媒の把持材として市販されている鉱物含有
成形体を用いてサイクル試験を行った。なお、鉱物含有
成形体は面密度0.278g/cm2 のセラミック繊維
を厚さ約4mmに圧縮してなるものである。加熱によっ
て、成形体内の有機バインダーが焼失し、厚さ方向に2
0mm程度まで膨張し、把持力を示すようになる。従っ
て、1サイクル目の室温では、成形体はクリアランスよ
りも小さいので、面圧を生じない。結果を表−2に示
す。Comparative Example 3 A cycle test was carried out using a mineral-containing compact which is commercially available as a holding material for a honeycomb type catalyst. The mineral-containing compact is obtained by compressing ceramic fibers having an areal density of 0.278 g / cm 2 to a thickness of about 4 mm. By heating, the organic binder in the molded body is burnt out, and
It expands to about 0 mm and exhibits gripping force. Therefore, at room temperature in the first cycle, the molded body is smaller than the clearance, so that no surface pressure is generated. The results are shown in Table-2.
【0018】[0018]
【表2】 [Table 2]
【0019】表−2中、800℃における面圧の値は、
左側が最高値、右側が降温直前の値を示す。表−2よ
り、本発明の把持材では、加熱、冷却をくり返しても十
分な面圧を示し、把持力を維持することができるが、鉱
物含有成形体では、加熱、冷却をくり返すと、成形体内
の繊維が劣化し、2サイクル目以降、800℃では面圧
を示さなくなり、把持力がなくなっていることが分か
る。In Table 2, the value of the surface pressure at 800 ° C. is
The left side shows the maximum value and the right side shows the value just before the temperature drop. From Table-2, the gripping material of the present invention shows sufficient surface pressure even if heating and cooling are repeated, and the gripping force can be maintained, but in the mineral-containing compact, when heating and cooling are repeated, It can be seen that the fibers in the molded body deteriorated, the surface pressure no longer exhibited at 800 ° C. after the second cycle, and the gripping force was lost.
【0020】実施例3 実施例1と同一の繊維からなり、ニードルパンチングが
施されているブランケットを800℃で24時間熱処理
して、面密度0.160g/cm3 のブランケットを得
た。このブランケットから、縦50×横50(mm)の
直方体の試料片を切り出し、室温において、厚さ方向に
圧縮し、厚さを4.6mmと4.9mmとに交互に増減
させ、面圧を測定した。1回の増減を1セットとし、1
0セット行った。結果を表−3に示す。Example 3 A blanket made of the same fibers as in Example 1 and subjected to needle punching was heat-treated at 800 ° C. for 24 hours to obtain a blanket having an areal density of 0.160 g / cm 3 . From this blanket, a rectangular parallelepiped sample piece having a length of 50 mm and a width of 50 (mm) was cut out, compressed in the thickness direction at room temperature, and the thickness was alternately increased and decreased to 4.6 mm and 4.9 mm to increase the surface pressure. It was measured. 1 increase / decrease is set as 1
I did 0 sets. The results are shown in Table-3.
【0021】実施例4 表−3に示す性質を有し、繊維径が約4μmである繊維
からなり、ニードルパンチングが施されているブランケ
ットを800℃で24時間熱処理した。このブランケッ
トを用いた他は、実施例3と同様に行った。結果を表−
3に示す。Example 4 A blanket having the properties shown in Table 3 and having a fiber diameter of about 4 μm and having needle punching was heat-treated at 800 ° C. for 24 hours. The same procedure as in Example 3 was carried out except that this blanket was used. Table of results
3 shows.
【0022】比較例4 比較例1と同一の繊維からなり、ニードルパンチングが
施されているブランケットを800℃で24時間熱処理
したものを用いた他は実施例3と同様に行った。結果を
表−3に示す。Comparative Example 4 The same procedure as in Example 3 was carried out except that a blanket made of the same fibers as in Comparative Example 1 and subjected to needle punching was heat treated at 800 ° C. for 24 hours. The results are shown in Table-3.
【0023】比較例5 比較例2と同一の繊維からなり、ニードルパンチングが
施されているブランケットを800℃で24時間熱処理
したものを用いた他は実施例3と同様に行った。結果を
表−3に示す。Comparative Example 5 The same procedure as in Example 3 was carried out except that a blanket made of the same fibers as in Comparative Example 2 and subjected to needle punching was heat treated at 800 ° C. for 24 hours. The results are shown in Table-3.
【0024】比較例6 比較例3と同一の鉱物含有成形体を800℃で24時間
熱処理したものを用いた他は実施例3と同様に行った。
結果を表−3に示す。Comparative Example 6 The same procedure as in Example 3 was carried out except that the same mineral-containing compact as in Comparative Example 3 was heat treated at 800 ° C. for 24 hours.
The results are shown in Table-3.
【0025】[0025]
【表3】 [Table 3]
【0026】表−3から、1セット目の厚さ4.6mm
のときの面圧が高く、かつ厚さの増減をくり返しても面
圧の低下が少ないものが、繊維の復元力が高く、把持材
に適する。From Table 3, the thickness of the first set is 4.6 mm.
The surface pressure at that time is high, and the surface pressure is less likely to decrease even if the thickness is repeatedly increased and decreased, but the fiber has a high restoring force and is suitable as a gripping material.
【0027】[0027]
【発明の効果】本発明によれば、長期間の使用において
も繊維の劣化が起こりにくく、長期的に安定な把持力を
発揮する把持材を得ることができる。According to the present invention, it is possible to obtain a gripping material that exhibits stable gripping force for a long period of time without causing deterioration of fibers even after long-term use.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 荘司 守 新潟県上越市福田町1番地 三菱化成株式 会社直江津工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Mamoru 1 Fukuda-cho, Joetsu City, Niigata Prefecture Mitsubishi Kasei Corporation Naoetsu Factory
Claims (3)
mm2 、直径45μm以上のショットの含有率が5重量
%以下、かつAl2 O3 /SiO2 (重量比)=70/
30〜74/26であるアルミナ繊維を積層し、かつニ
ードルパンチングによりその繊維の一部を積層面に対し
て縦方向に配向させてなるブランケットで構成したこと
を特徴とする排ガス浄化装置用把持材。1. A single fiber tensile strength of 150 to 400 kg /
The content of shots having a diameter of mm 2 and a diameter of 45 μm or more is 5% by weight or less, and Al 2 O 3 / SiO 2 (weight ratio) = 70 /
A gripping material for an exhaust gas purifying apparatus, which is composed of a blanket formed by laminating alumina fibers of 30 to 74/26 and by orienting part of the fibers by needle punching in a longitudinal direction with respect to a laminating surface. .
あることを特徴とする請求項1に記載の排ガス浄化装置
用把持材。2. The gripping material for an exhaust gas purifying apparatus according to claim 1, wherein the crystallinity of the alumina fiber is 0 to 10%.
いるハニカム型触媒との間隙に、請求項1又は2記載の
把持材を介装してなる内燃機関の排ガス浄化装置。3. An exhaust gas purifying apparatus for an internal combustion engine, wherein the gripping material according to claim 1 is interposed in a gap between a catalyst casing and a honeycomb type catalyst housed therein.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP07763994A JP3282362B2 (en) | 1994-04-15 | 1994-04-15 | Grasping material for exhaust gas purification equipment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP07763994A JP3282362B2 (en) | 1994-04-15 | 1994-04-15 | Grasping material for exhaust gas purification equipment |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07286514A true JPH07286514A (en) | 1995-10-31 |
JP3282362B2 JP3282362B2 (en) | 2002-05-13 |
Family
ID=13639471
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JP07763994A Expired - Lifetime JP3282362B2 (en) | 1994-04-15 | 1994-04-15 | Grasping material for exhaust gas purification equipment |
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